Article(id=1172619712019182202, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172619710446321994, articleNumber=1009-2617(2024)03-0215-09, orderNo=null, doi=10.13355/j.cnki.sfyj.2024.03.001, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1679068800000, receivedDateStr=2023-03-18, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1757503925566, onlineDateStr=2025-09-10, pubDate=1718812800000, pubDateStr=2024-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1757503925566, onlineIssueDateStr=2025-09-10, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1757503925566, creator=13701087609, updateTime=1757503925566, updator=13701087609, issue=Issue{id=1172619710446321994, tenantId=1146029695717560320, journalId=1146120122248306696, year='2024', volume='43', issue='3', pageStart='215', pageEnd='340', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1757503925191, creator=13701087609, updateTime=1758768108393, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1177922079165923462, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172619710446321994, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1177922079165923463, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1172619710446321994, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=215, endPage=223, ext={EN=ArticleExt(id=1172619712258257531, articleId=1172619712019182202, tenantId=1146029695717560320, journalId=1146120122248306696, language=EN, title=Research Progress on Recovering Ruthenium from Ruthenium-Containing Waste, columnId=1152626642049446094, journalTitle=Hydrometallurgy of China, columnName=Reviews, runingTitle=null, highlight=null, articleAbstract=

Recovering and reusing ruthenium from platinum group metal waste has great influence on sustainable development, resource conservation and environmental protection. Ruthenium waste generally includes ruthenium-containing waste catalysts, ruthenium-containing alloy materials, ruthenium-containing nuclear waste and other ruthenium-containing waste. The comprehensive recovery and treatment methods of different ruthenium wastes are summarized. The processes of transforming soluble salts by oxidative distillation, melting-reduction-oxidation, melting-oxidation-distillation, microwave leaching-cloud point extraction, distillation-melting-reduction, melting-reduction-oxidation, ion exchange, oxidation volatilization, electrolysis, biosorption and physical adsorption are introduced respectively. The advantages and disadvantages of existing ruthenium waste recovery technologies are summarized. And the development direction of ruthenium waste recovery technology in the future is prospected.

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从铂族金属废料中回收再利用钌对于实现行业可持续发展、节约资源和环境保护都有着重大影响。钌废料一般包括含钌废催化剂、含钌合金材料、含钌核废料和其他含钌废料等。综述了不同钌废料的综合回收处理方法,分别介绍了氧化蒸馏法转化可溶性盐、熔融—还原—氧化法、熔融—氧化—蒸馏法、微波浸出—浊点萃取法、蒸馏—熔融—还原法、熔融—还原—氧化法、离子交换法、氧化挥发法、电解法、生物吸附法和物理吸附法等工艺,总结了现有钌废料回收技术的优缺点,并对未来钌废料回收工艺的发展方向进行了展望。

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陈丽杰(1992—),女,博士研究生,助理研究员,主要研究方向为贵金属冶金、二次资源回收利用。E-mail:
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刘忆(1999—),男,硕士研究生,主要研究方向为湿法冶金、二次资源回收利用。

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刘忆(1999—),男,硕士研究生,主要研究方向为湿法冶金、二次资源回收利用。

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从含钌废料中回收钌的研究进展
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刘忆 1 , 王才平 2 , 田磊 1 , 李金辉 1 , 王翀 2 , 郁丰善 3 , 陈丽杰 1
湿法冶金 | 综合评述 2024,43(3): 215-223
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湿法冶金 | 综合评述 2024, 43(3): 215-223
从含钌废料中回收钌的研究进展
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刘忆1, 王才平2, 田磊1, 李金辉1, 王翀2, 郁丰善3, 陈丽杰1
作者信息
  • 1 江西理工大学 冶金工程学院, 江西 赣州 341000
  • 2 横峰县凯怡实业有限公司, 江西 上饶 335500
  • 3 江西省君鑫贵金属科技材料有限公司, 江西 上饶 335500
  • 刘忆(1999—),男,硕士研究生,主要研究方向为湿法冶金、二次资源回收利用。

通讯作者:

陈丽杰(1992—),女,博士研究生,助理研究员,主要研究方向为贵金属冶金、二次资源回收利用。E-mail:
Research Progress on Recovering Ruthenium from Ruthenium-Containing Waste
Yi LIU1, Caiping WANG2, Lei TIAN1, Jinhui LI1, Chong WANG2, Fengshan YU3, Lijie CHEN1
Affiliations
  • 1 School of Metallurgical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China
  • 2 Hengfeng Kaiyi Industrial Co., Ltd., Shangrao 335500, China
  • 3 Jiangxi Junxin Precious Metal Technology Materials Co., Ltd., Shangrao 335500, China
出版时间: 2024-06-20 doi: 10.13355/j.cnki.sfyj.2024.03.001
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从铂族金属废料中回收再利用钌对于实现行业可持续发展、节约资源和环境保护都有着重大影响。钌废料一般包括含钌废催化剂、含钌合金材料、含钌核废料和其他含钌废料等。综述了不同钌废料的综合回收处理方法,分别介绍了氧化蒸馏法转化可溶性盐、熔融—还原—氧化法、熔融—氧化—蒸馏法、微波浸出—浊点萃取法、蒸馏—熔融—还原法、熔融—还原—氧化法、离子交换法、氧化挥发法、电解法、生物吸附法和物理吸附法等工艺,总结了现有钌废料回收技术的优缺点,并对未来钌废料回收工艺的发展方向进行了展望。

铂族金属废料  /  钌  /  废催化剂  /  合金材料  /  核废料  /  回收技术  /  研究进展  /  展望

Recovering and reusing ruthenium from platinum group metal waste has great influence on sustainable development, resource conservation and environmental protection. Ruthenium waste generally includes ruthenium-containing waste catalysts, ruthenium-containing alloy materials, ruthenium-containing nuclear waste and other ruthenium-containing waste. The comprehensive recovery and treatment methods of different ruthenium wastes are summarized. The processes of transforming soluble salts by oxidative distillation, melting-reduction-oxidation, melting-oxidation-distillation, microwave leaching-cloud point extraction, distillation-melting-reduction, melting-reduction-oxidation, ion exchange, oxidation volatilization, electrolysis, biosorption and physical adsorption are introduced respectively. The advantages and disadvantages of existing ruthenium waste recovery technologies are summarized. And the development direction of ruthenium waste recovery technology in the future is prospected.

platinum group metal waste  /  ruthenium  /  spent catalyst  /  alloy material  /  nuclear waste  /  recycling technology  /  research progress  /  prospect
刘忆, 王才平, 田磊, 李金辉, 王翀, 郁丰善, 陈丽杰. 从含钌废料中回收钌的研究进展. 湿法冶金, 2024 , 43 (3) : 215 -223 . DOI: 10.13355/j.cnki.sfyj.2024.03.001
Yi LIU, Caiping WANG, Lei TIAN, Jinhui LI, Chong WANG, Fengshan YU, Lijie CHEN. Research Progress on Recovering Ruthenium from Ruthenium-Containing Waste[J]. Hydrometallurgy of China, 2024 , 43 (3) : 215 -223 . DOI: 10.13355/j.cnki.sfyj.2024.03.001
铂族金属(Platinum group metals,PGMs)包括Pt、Pd、Rh、Ru、Ir、Os六种元素,广泛应用于信息产业、制药行业、航天事业、催化等多个领域[1],需求量逐年提高。但我国铂族金属远景储量低于350 t,资源匮乏,开采难度大,成品品位也较低,因此,大量依赖进口,对外依存度达98%以上[2-5]
钌(Ru)作为铂族金属的一种,由于其发展时间短且在我国的研究起步也较晚,其工业化应用相对于其他铂族金属较少[2]。但随着对钌的研究越来越深入,钌基催化剂在有机和催化领域表现出了独特和稳定的催化性能,有望作为铂基催化剂的替代。在生物医学领域,医疗靶材通常采用铂族金属。相较而言,以铂为靶材的抗肿瘤药物不仅副毒作用大,价格也极其昂贵;而钌价格相对较低,工艺可控性相对更强,成本更低,因此,以钌为靶材的抗癌药物研发日益受到关注[6-7]。随着新型钌基材料的研发,钌纳米材料和钌类催化剂等产品需求量也逐年增大[8-9]。铂族金属是不可再生资源,因此,从二次资源中回收钌,已成为维护国家资源安全的重点方向。本文综述了从含钌废料中回收钌的主要工艺,并对钌二次资源回收的发展前景进行了展望。
目前,我国钌的储备极度不足,对于钌资源的二次循环利用重视程度还不够,但随着钌的应用领域逐步扩大,预计今后钌需求量会逐渐增大。因此,研究钌二次资源的回收对我国钌行业的发展有深远意义。
钌废料主要包括含钌废催化剂、含钌合金材料、含钌核废料等[10-11]。处理含钌废催化剂的方法一般包括氧化蒸馏法转化可溶性盐、熔融—还原—氧化法、熔融—氧化—蒸馏法及微波浸出—浊点萃取法;处理含钌合金材料的方法一般包括蒸馏—熔融—还原法、熔融—还原—氧化法、吸附法、萃取法、高温熔炼法、活泼金属置换法[12-15];处理含钌核废料的方法一般包括离子交换法、氧化挥发法和电解法。此外,生物吸附法和物理吸附法也是回收钌废料中钌的常见工艺。
以负载型钌催化剂为例,主要有活性炭负载型钌催化剂和氧化铝负载型钌催化剂。钌可直接用作催化剂,也可负载在其他催化剂基体上,形成具有较高催化活性的复合催化剂[16]。通常,用作回收含钌废催化剂中钌的主要工艺有氧化蒸馏法、微波浸出—浊点萃取法等[5]
目前对含钌废催化剂常用的处理工艺是酸溶后焙烧富集、碱溶造液再氧化蒸馏,用盐酸吸收后浓缩蒸干得到成品三氯化钌。氧化蒸馏法中的熔融—氧化—蒸馏法是目前最全面的工业化回收钌的方法之一[5,17]。火法工艺成熟,操作简单,但消耗大,要求高温,对后续的分离提纯要求也较高。所以,寻求一种高效的废催化剂回收贵金属技术迫在眉睫。
氧化蒸馏法是回收钌常用工业化方法之一。由于四氧化钌沸点为108 ℃,在较低温度下即可挥发;因此,将钌用氧化剂氧化成四氧化钌,进而借助其低沸点的性质加热挥发,再将挥发出的气体通入盐酸溶液中,即可得纯度较高的三氯化钌溶液,经过浓缩烘干得水合三氯化钌。氧化蒸馏法主要有:酸/碱性体系下的氧化蒸馏法、熔融—氧化—蒸馏法和直接氧化法[4]
王杰等[18]研究了一种从含钌、铱废催化剂中分离回收钌、铱的方法。首先向废催化剂中通入氯气进行氯化焙烧,加入盐酸反应,过滤得含钌渣;渣与过氧化钠、氢氧化钠碱熔,得含钌钠盐;再通入氯气进行蒸馏,将蒸馏产物通入钌吸收液中,加入卤酸钠溶液氧化蒸馏,将蒸馏产物通入钌吸收液中,分别得含钌溶液和含铱溶液。加入氯化铵得氯钌酸铵,还原得海绵钌,其工艺流程如图1所示。
江莉龙等[19]研究了一种从可溶性钌酸盐中回收活性炭负载钌废催化剂中钌的方法,其工艺流程如图2所示。首先对物料进行预处理,预处理过程主要是利用酸液将废料中的碱金属等物质洗脱;之后向废料中加入碱金属化合物进行火法焙烧,即将钌转化为钌酸盐,同时催化活性炭的氧化,大幅降低焙烧温度,缩短焙烧时间;后处理步骤可将多羟基醇与碱金属钌酸盐配合,生成多羟基醇钌配合物,抑制碱金属钌酸盐分解,提高钌回收率。该法流程简单,且焙烧时间短,能耗低。
倪军等[20]研究了从一种活性炭负载钌废催化剂中回收钌的方法。首先将催化剂放置在100~130 ℃烘箱内干燥,再进行高温焙烧除去废钌炭催化剂中的炭载体,之后将焙烧后的固体加入到过量10%的乙酸溶液中浸渍,过滤得二氧化钌。该法工艺简单,能将钌废催化剂中的钌有效转化为碱金属钌酸盐进入溶液中,但有机溶液的分离效果有待提升。
刘利等[21]研究了采用熔融—氧化—蒸馏法回收氧化铝负载钌废催化剂中的钌。结果表明:以氢氧化钾或硝酸钾作碱熔剂、硫酸和氯酸钠为氧化剂,在反应温度650 ℃、反应时间2.5 h条件下对废催化剂进行碱溶,之后将温度设置为80 ℃,再进行减压蒸馏1.5 h,钌回收率可达93%。工艺流程如图3所示。
钌的特性非常稳固,在强酸和王水中的耐腐蚀性极强,可通过微波加热溶解钌。Suoranta等[22]研究了微波浸出—浊点萃取法回收氧化铝负载钌废催化剂中的钌。首先取0.1 g贵金属渣物料4组(1组用于测定温度和压力),加入1 mL浓盐酸、6 mL浓硝酸、1 mL氢氟酸,加入微波消解仪中进行消解,在90~210 ℃条件下,钌回收率在89%~96%之间;然后采取浊点萃取分离浸出液中的钌,以2-巯基苯并噻唑作(C7H5NS2)为配合剂、Triton X-100(C14H22O(C2H4O)n,n=9~10)为表面活性剂进行萃取,钌的最终单级萃取率为66%~77%。工艺流程如图4所示。
该法具有可控性好、受热均匀、容器密闭性好等优点;但每次最多同时处理8个消解罐,其中还有1个作为控制罐无法使用,目前还仅停留在实验室研究阶段。
熔融—还原—沉淀法包括预处理、碱溶、浸出、还原沉淀、溶解和浓缩烘干等工序。预处理过程包括洗涤烘干、焙烧、球磨、氢气还原等。首先将废加氢催化剂中部分杂质洗脱,之后在球磨机中球磨至细粉颗粒(75~150 μm),取出进行焙烧除去少量积碳或者碳载体[23]。碱熔过程为火法碱焙烧,原理与熔融—氧化蒸馏法的原理相似。碱溶后将碱溶渣进行水浸,用热水冲滤,通过向水浸液中加入乙醇进行还原得氢氧化钌沉淀,沉淀后液返回碱溶渣的水浸液中,将氢氧化钌减压蒸馏后得水合三氯化钌,最后向水合三氯化钌中通入氢气还原,便可得钌粉。该工艺将火法焙烧和湿法酸溶相结合,在溶解铂族金属废料上应用非常广泛,且工艺成熟。熔融—还原—沉淀法工艺流程如图5所示。
熔融—还原—沉淀法能处理多种物料,具有广阔的应用前景。此外,还有高温熔炼法、活泼金属置换法,但由于相关应用较少,本文不做详述。
钌合金主要包括钼钌合金、铂钌合金、铱钌合金、钽钌合金及硅钌合金[24-28]。氧化蒸馏法是利用氧化剂将钌合金中的钌氧化成熔沸点低、易挥发的四氧化钌加以回收。但四氧化钌为强氧化剂,遇低分子有机物会爆炸,且会释放剧毒气体,对人体造成伤害。因此,研究一种绿色、高效的回收钌的方法具有重要意义。从合金材料中回收钌的工艺主要有蒸馏—熔融—还原法和熔融—还原—氧化法[5,29-32]
赵喜太[33]研究了采用蒸馏—熔融—还原法回收废计算机硬盘的含钌合金废料。采用两段式盐酸分离贱金属,分别在6 h和2 h分离含钌废料中的钌,用硫酸加氯酸钠蒸馏精炼含钌合金废料;将蒸残渣放入坩埚中,加入过氧化钠和氢氧化钠,混匀后将坩埚置于马弗炉中,并于700 ℃下碱熔1 h;冷却至室温后用热水冲洗溶解,加热搅拌,待溶解完毕后,过滤液直接用甲酸还原,滤渣重新返回进行蒸馏;选用盐酸/氯化钠溶液作为钌的吸收液,用甲酸还原法从吸收液中分离提取钌,最后将产物直接进行氢还原得到钌粉,蒸馏—熔融—还原法工艺流程如图6所示。
熔融—还原—氧化法是贵金属回收的常用工艺之一,首先是将原料进行高温焙烧,在熔融状态下贵金属会与贱金属形成合金,进而使浸出流程更易进行,加酸浸出后所得富集料经还原后可得到钌。
王皓等[34]提出了一种熔融—还原—氧化法从废雷尼催化剂中回收钌和铑的方法。首先向失效的雷尼镍催化剂中加入碳酸钠粉末混合均匀后放入电阻炉内焙烧,焙烧温度800~900 ℃、焙烧时间1~2 h;焙烧后的混合物料中加入纯水,并在50~60℃下水浸2~3 h,过滤、洗涤,得浸出液和浸出渣,浸出液外排至废水处理系统,浸出渣备用;向浸出渣中加入浓度为4~5 mol/L稀硫酸,在温度85~95 ℃下浸出4~6 h,得脱镍浸出液和贵金属富集料;向脱镍浸出液中加入草酸,产生草酸镍沉淀,草酸加入量为脱镍浸出液中镍含量的1.2~1.5倍;富集料经过氯化、精制后得海绵钌。其工艺流程如图7所示。
许莉等[35]研究了用含钌废催化剂制备固体亚硝酰硝酸钌[Ru(NO)(NO3)3)]。将含钌废催化剂干燥后与碳酸钠混合焙烧,焙烧渣通氢气还原;将还原渣在空气中氧化成四氧化钌气体后用硝酸溶液吸收;吸收后溶液用乙醚进行萃取,萃余液返回硝酸溶液吸收,有机相中的乙醚蒸发得亚硝酰硝酸钌。工艺流程如图8所示。
熔融—还原—氧化法的优点在于工艺流程简单,相较于蒸馏氧化还原更易实现工业化,可处理大量废料,但缺点在于空气氧化速率慢,回收率较低。
核电站反应堆中236U的衰变链含有铑、钯、银、锆、钌、钼、锝、钌等贵金属,根据产生核素的机制可分为“锕系元素”和裂变产物[36],这些核废料被称为“乏燃料”。Ru元素的同位素及丰度为:96Ru(5.51%)、98 Ru(1.87%)、99Ru(12.72%)、100Ru(12.62%)、101Ru(17.07%)、102Ru(31.61%)、104Ru(18.58%)[37-39]。Ru有99-106Ru多种同位素,除了具有放射性的103Ru和106Ru(半衰期分别为39d和368 d)外,其他的是稳定同位素[40]
乏燃料中的钌、铑、钯被称为“裂变假铂—FPs (fission platinoids)”[41]。全世界每年排出的乏燃料中含有钌22.5 t、铑3.7 t、钯15 t[42]。浸出液中FPs应以[RuNO(OH)(NO2)4]2-、[Rh(NO2)6]3-、Pd(NO3)2等状态存在,常见的处理方法有离子交换法、氧化挥发法、电解法、还原沉淀法及溶剂萃取法等[38,43]
离子交换法是液相中电离的离子受到吸引靠近被喜好的离子交换剂,并在离子交换剂表面完成离子交换,但由于溶液中电荷发生变化,离子交换剂上的同种电荷离子又会进入到液相中,因此溶液会继续保持中性,而液固两相中发生离子交换。
Banjarnahor等[44]研究了一种新型无机离子交换剂磷钼酸钨(WMP)的合成,并将其二氧化硅负载型WMP-Si用于去除和回收乏核燃料中的钌和铯元素,这2种离子交换剂均由磷钼酸和钨酸铵通过真空浸渍法用真空蒸发器合成。在用高浓度硝酸洗涤后,钌被洗脱,铯则保留在WMP-Si中,说明用WMP-Si可有效实现铯和钌的富集和分离。
Kumar等[45]使用Chromosorb W(二甲基二氯硅烷)处理的酸洗硅藻土二氧化硅的萃取色谱树脂(ECR),负载有季铵化合物Aliquat 336。最优条件下进行的色谱柱研究显示,在第1次循环中钌回收率约为82%,而后急剧下降至60%。Du Z.Y.等[46]针对废旧锂电池中有价金属离子的分离回收,开发了一种原位电浸出与电化学交换离子交换耦合的绿色新工艺。结果表明,与粉末浸出相比,原位电浸出具有明显优势。
离子交换法是相对较易实现工业化的方法之一,但离子交换剂吸附能力强弱不同,目前还没有吸附效果较令人满意的离子交换剂。
氧化挥发法是一种乏燃料中回收裂变假铂中同位素钌的常规工艺,利用钌沸点低的特性,蒸馏分离钌进而对吸收液中钌进行回收。
Liu J.Z.等[47]研究了Mo0.231Ru0.558Pd0.123Rh0.088合金粉末的氧化和蒸发行为。结果表明:金属钌粉末的蒸发损失率随各种钌氧化物气体的总蒸汽压增加而增大;对于合金粉末,由于形成的钼和二氧化钼氧化还原电对控制了较低的氧分压,从而延缓了钌的氧化和蒸发;在钼释放后,钌-钯-铑合金粉末中钌的蒸发损失率会直接受到合金中钌活性的影响。
杨深宏等[48]提出了一种从失效钌锌催化剂中回收钌的方法,在采用常规的焙烧和碱溶工艺后再对废料进行氯气蒸馏,在最优条件下,钌直接回收率可达97.66%。
氧化挥发法的优点在于工艺流程短,回收率高,所需原料简单、设备结构简易;缺点在于乏燃料中有大量对人体有害的放射性元素,在氧化挥发过程中须确保装置的气密性,否则可能对人体造成严重伤害。
电解法是通过直流电将物质的电子进行定向移动,进而引起物质的化学变化的方法,通常在电解槽中进行。
Jayakumar等[49]研究了用电解法回收含三价钌、三价铑和二价钯(各60 mg)的模拟高放射性废液(SHLLW)中的钌。结果表明:在铂和不锈钢电极下进行模拟,钌和铑回收率在10%左右,而铂回收率在80%左右;3个阴极负电位分别在-0.5、-0.7、-1.0 V下,钌回收率分别为9.3%、7.7%、12%。说明随阴极电位增加,钌浸出率也逐渐提高,但关于电解法回收钌的工艺还有待进一步研究。
Swain等[50]研究了采用电氧化法从亚硝基亚硝酸和模拟高水平废液(SHLLW)中分离RuO4气体。结果表明:采用电氧化法从亚硝基硝酸和SHLLW中可分别分离出95%和54%的Ru;为了最大限度减少亚硝酸盐离子的有害影响,设计了一个以玻璃融块为隔膜的分裂池,在没有任何催化剂情况下,在(313±2) K的亚硝基硝酸和SHLLW溶液中分离出75%和80%的Ru。
电解法的优点是回收流程简短,将处理好的废料倒入电解槽中电解即可;缺点是若要电解出对应的金属,须对电压进行精准把控,而电压的控制较为困难。
生物吸附法是利用微生物中细菌等生物作吸附剂来吸附离子或化合物的方法。
Giovanni等[51]首次证明了以紫色非硫细菌(PNSB)为微生物吸附剂去除和部分回收工业废水中钌的可能性,结果表明,从生物质中回收钌量为PNSB吸附量的42%~72%。
Kwak等[52]制备了聚乙烯亚胺(PEI)改性的细菌生物吸附纤维(PBBF)并用于吸附钌,结果表明,PBBF对钌的最大吸附量可达110.5 mg/g,而原始生物质和商用离子交换树脂Lewatit Mono Plus M600对钌的吸附量分别为16.0、6.7 mg/g,PBBF对钌的吸附性能更优。
生物吸附法的优点是操作简单,可降低采矿对环境的影响;缺点是细菌的培养过程长,在不同环境下吸附量不同,且对于不同废料的吸附量也不同,回收率相对较低。
物理吸附法是利用物质的物理特性,即材料与物质之间的电荷平衡、渗透压等维持物质吸附状态的方法。
Zhang S.C.等[53]研究了用微孔硅聚物isoBu-BTP/SiO2-P吸附剂从模拟电镀废水中分离三价钌。结果表明:isoBu-BTP/SiO2-P具有选择性高(SFRu/其他金属>35)、吸附量大(54.6 mg/g)、吸附速度快等优点,isoBu-BTP/SiO2-P对钌的吸附符合准二级动力学模型和Langmuir等温吸附模型;柱实验结果表明,钌与模拟电镀废水中的其他金属离子可有效分离;在整个吸附过程中,磷官能团(P══O)和三价钌之间存在强烈的相互作用,同时阴离子基团(NO3和NO2)参与维持电荷平衡。isoBu-BTP/SiO2-P在回收电镀废水中的钌方面具有一定潜力。
Serdar等[54]研究了用锌粉通过胶结反应从废液中回收钌,采用多种数学动力学模型,通过拟合计算得到胶结作用的活化能为12.48 kJ/mol,在65 ℃下加入1 000 mg氯化钠,钌回收率超过95%。
Klug等[55]和Wang X.P.等[56]研究了异丁基BTP/二氧化硅-磷在硝酸介质和硝酸钠介质中对微量锕系元素的吸附行为,结果表明:异丁基BTP/二氧化硅-磷吸附选择性能良好。Ning S.Y.等[57]研究了异丁基BTP/二氧化硅-磷在硝酸盐溶液中对钌、铑、钯的吸附、解吸和分离行为,重点考察了对钌和铑的吸附、解吸和分离行为。结果表明:在25 ℃下,异丁基BTP/二氧化硅-磷吸附剂在较宽的硝酸钠浓度范围(0.5~5 m)内具有良好的吸附性能,在低于55 ℃范围内,随温度升高,钌和铑吸附率显著提高,二者在0.1 mol/L HNO3-3 mol/L NaNO3溶液中的吸收率大于98%。
物理吸附的优点是吸附和解吸效果好,回收率高,选择性好。缺点是物理吸附剂单次仅能吸附少量废料,废料量较大时,吸附率明显降低。
含钌废料主要分为含钌废催化剂、含钌合金材料、含钌核废料等,针对不同种类的含钌废料回收工艺也不同。与火法回收工艺相比,湿法回收工艺具有成本较低、温度条件低、金属回收率高等优点,在含钌废料回收中应用更广泛。
1)针对含钌废催化剂的回收,主要有氧化蒸发法、转化可溶酸性盐、熔融—还原—氧化法、熔融—氧化—蒸馏法以及微波浸出—浊点萃取法。4种方法中,以氧化蒸发法工业化最普遍,微波浸出—浊点萃取则在实验室研究中应用较多,而转化可溶酸性盐应用于活性炭负载钌催化剂,熔融氧化蒸馏应用于氧化铝负载钌催化剂,熔融—还原—沉淀法应用于废加氢催化剂。
2)钌合金主要包括钼钌合金、铂钌合金、铱钌合金、钽钌合金及硅钌合金,应用较多的回收工艺为蒸馏—熔融—还原法、熔融—还原—氧化法。由于合金的种类繁多,在浸出时须考虑后续分离提纯,因而针对不同的合金材料选用不同的回收工艺。
3)从含钌核废料中回收同位素钌通常采用离子交换法、氧化挥发法和电解法。其中,离子交换法可控性好,成本低,效果显著,是一项可靠的工艺;氧化挥发法适用范围广,对设备要求低;而电解法对设备要求高,能源消耗高,目前应用较少。
4)除此之外,生物吸附法利用细菌对钌进行回收,物理吸附法利用二氧化硅等多孔材料对钌进行吸附回收,这些回收工艺均能够有效回收钌,具有一定的发展潜力。
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2024年第43卷第3期
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doi: 10.13355/j.cnki.sfyj.2024.03.001
  • 接收时间:2023-03-18
  • 首发时间:2025-09-10
  • 出版时间:2024-06-20
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  • 收稿日期:2023-03-18
基金
国家自然科学基金资助项目(52064021)
江西省自然科学基金重点项目(20232ACB204016)
江西省主要学科学术与技术带头人-青年人才培养计划(20204BCJL23031)
上饶市“揭榜挂帅”项目科技计划(2022A005)
横峰县凯怡实业有限公司横向课题(2022360702007502A)
江西理工大学清江青年英才支持计划(JXUSTQIBI2020004)
作者信息
    1 江西理工大学 冶金工程学院, 江西 赣州 341000
    2 横峰县凯怡实业有限公司, 江西 上饶 335500
    3 江西省君鑫贵金属科技材料有限公司, 江西 上饶 335500

通讯作者:

陈丽杰(1992—),女,博士研究生,助理研究员,主要研究方向为贵金属冶金、二次资源回收利用。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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